The synchronous use of Infrared (IR at 1064nm) and Ultraviolet (UV at 355nm) wavelengths of a Q-Switched Nd:YAG laser has been shown to efficiently confront the issue of discoloration, which may be observed upon laser ablation of environmental encrustation from marble surfaces, and thus this methodology is effectively employed in various laser cleaning applications. In order to further investigate the mechanisms that influence this result, a series of tests were undertaken on fragments of marble with environmental homogeneous compact crust. Through a number of irradiation tests applying a variety of laser parameters (individual use of IR and UV beams, as well as, their synchronous use) the different ablative processes have been investigated. In this paper, micro-Raman and Laser Induced Breakdown Spectroscopy (LIBS) were employed in order to examine the role of each laser beam, as well as their combination, and so to approach the reasons that induce yellow discoloration. The results of the above studies will be presented with the aim to further describe the two wavelength laser cleaning methodology and its principle, thus elucidating its effectiveness.